Method of stopping leaks



Nov. 24, 1942. H. A. RVEIMERS 2,302,913

METHOD OF STOPPING LEAKS Filed Aug. 31, 1939 B Sheets-Sheet l M ATTORNEYS Nov. 24; 1942. H.A.REI MERS 2,302,913

METHOD OF STOPPING LEAKS Filed Aug. 31, 1959 8 Sheets-Sheet 2 WA WMMAA 0 NW 4 V W W v v INVENTQR Hans ,4. ge/mens M MZ ATTORNEYS NOV.24, 1942. v ME I 2,302,913

METHOD OF STOPPING LEAKS Filed Aug. 31, 1939 8 Sheets- Sheet 3 A6205 ,4. {whens w ATTORNEYS Nov. 24, 1942. H. A. REIMERS 2,302,913

METHOD DI STOPPING LEAKS Filed Aug. 51, 1959 8 Sheets-Sheet 4 mm vmm 1mm 77 a V a @MA/VW Q $5 WOMAAAAAAOAAM- &

- INVENTOR Hans 4. Qezmens Mum! ATTORNEYS Nov. 24, 1942. v RElMERs 2,302,913

' METHOD OF STOPPIHNG LEAKS Filed Aug. 31, 1959 8 Sheets-Sheet 5 INVENTOR flu 0.5 A. ,Qg/mers ATTORNEYS Nov. 24 1942. H, A, REMERS 2,302,913

METHOD 7 OF STOPPING LEAKS Filed'Aug; 31, 1939 8 Sheets-Sheet e ATTORNEYS Nov. 24; 1942. H. A. RElMERS I ,3 2,

METHOD OF STOPPING LEAKS I Filed Aug. 31, 1959 8 Sheets-Sheet 7 INVENTOR 16 0/75 4. @e/mecs ATTORNEYS Nov. 24, 1942. H. A. REIMERS 2,302,913

METHOD OF STOPPING LEAKS Filed Aug. 51, 1959 8 Sheets-Sheet 8 mvEyTOR 16 4/75 A. .Qe/mer-J ATTORNEYS able matter for its operation.

non-sealing until subjected to electrolysis.

.jects and advantages will tion proceeds."

' Patented Nov. 24,1942

UNITED STATES" PATENT} OF ICE Mnrnon F s'rorrma LEAKS Hans A. Reimers, Midland, Mich, assignoriof one-third to James Mich, and one-third Midland, Mich.

Application August 31,

deposit in'situ when introduced into alea'k andho re e. there subjected to electrolysis, which deposit bonds itself firmly] to the surface of the leaking part, thereby forming a substantially permanent leak repair capable of strongly resisting displacement by fluid-pressure.

' Another object is to provide an aqueous liquid leak-stopping composition that does not require the presence therein of suspended filter- Another object is to provide an aqueous leakstopping' composition which may be used effectively in the presence of water and does not require air-drying for its operation.

Another object is to provide an aqueous liguid leak-stopping composition that does not detericrate in ordinary usage and the unusedportion thereof is capable of reuse.

Another objectis to provide an aqueous liquid leak-sealing composition that remains liquid and A further object is to provide a method of I stopping up leaks whereby the so stopped up leak- I may be subjected to a moderate amount oi. flexing without destroying the seal. Still other obappear as the descrip I have discovered that by'mixing an aqueous solution containing a-water-soluble silicate and an aqueous solution of one of the water-soluble inorganic metal salts ofaluminum, cadmium,

trivalent chromium, divalent copper, trivalent iron, divalent manganese, trivalent tin, and zinc in certain proportions, hereinafterset forth, mobile solutions (i. e. solutions which are substantially free from filterable precipitates or jellies) are obtained which are capable 01. sub-- stantially completely passing through ordinary filter paper and normally remain in this state apparently indefinitely, but when subjected to' electrolysis have the property of depositing a water-resistant semi-rigid gel in contact with the anode. I havefurther discovered that by maintaining such solution in contact with that portion of a vessel conduit, pipe, or the like having a leak to be repaired and bringing about W. Bebbeck, Freeland, to Thomas Griswold, Jr.,

1939, Serial No. 292,916 (or. 138-97) electrolysis of the solution in situ, a semi-rigid gel is formed over and in the leak effectively sealing it. The sealing deposit so obtained is impervious to fluids, has the advantage of being slightly flexible yet not easily displaced when subjected to mechanical strain. After the sealing deposit is produced, the excess solution not transformed into the gel may be removed and stored, preferably in a wooden or glass vessel, for

for and method of stopping leaks hereinafter fully described and particularly pointed out in the claims, reference being had to the accompanying drawings illustrating various embodi? ments of the invention.

In the said annexed drawings v W Fig. 1 is a portion of a triangular diagram showing a graph of the proportions of water, sodium" silicate, and aluminum sulphate in my leak-stopping composition plotted with triangular co-ordinates. v

Fig. 2 is a similar diagram showing the proportions of water, sodium silicate, and cadmium sulphate.

Fig. 3 is a similar diagram showing the proportions of water, sodium silicate, and cupric chloride.

Fig. 4 is a similar diagram showing the proportions of water, sodium silicate, and chromium sulphate. i

Fig. 5 is a similar diagram showing the proportions of water, ride. 00 Fig. 6 is a. similar diagram showing the proportions 'of water, scdium silicate, and manganous sulphate.

Fig. 7 is a similar diagram showing the proportions of water, sodium silicate, and stannic chloride. Fig. 8 is asimilar diagram showing the proportions of water, sodium silicate, and zinc sulphate. The method of plotting the proportions of the ingredients in the composition is that proposed by Gibbs, Trans, Conn. Acad, 1876, vol. 3, page 176. ,In this method the corners ofthe triangle represent 100 per cent of each of the ingredients and the relative, proportions or percentages 01' the three ingredients in any ternary mixture of them are read along the perpendicular line drawn from the side of the triangle opposite the comer'representingthe ingredient to the point in the triangle representing the mixture or m o ti V. V.

Since -iii'anost'iof the compositionashown on the Theinvention then consists of the composition sodium silicate, and ferric chlodiagrams a relatively high percentage ot water may be present with a relatively small percentage of the other two ingredients only that portion oi the triangle is shown which issuflicient to completely represent the range of proportions or the ingredients for the leak-stopping solutions illustrated. Referring to Fig. 1 for an illustration of the method or reading the diagrams, the

point P may be selected by wayof example. As

shown, the perpendicular distance of the point P from the bottom or horizontal, side 0! the triangle (which is foreshortened and, therefore, not shown) is 90 per cent as indicated by the perpendicular scale and, being opposite the water corner, represents the per cent of water. yrne perpendicular distance of the point P from the left hand side of the triangle similarly represent:

'9 per cent of aluminum sulphate, and the perpendicular distance oi the point? from the right hand side presents l per cent of sodiumsillcate o '(Na:O.3.2Si0r). The percentage composition oi any other point is read in similar manner, reference being made in each-case to the percentage scales shown. p M In compounding the leak-stopping solutions according to the invention it is preferable to first make a stock solution of the soluble silicate and ,ot the metal salt to be used, each in a suitable concentration so that by suitably diluting the stock 'solutiiins and then mixing these the so desired leak-stopping solution is obtained. For thefsoluble silicate I may use an alkali metal silicate, such as potassium or sodium silicate, preferably the latter, generally in a concentrabe prepared by adding a stock sodium silicate solution, diluted to the proper concentration, to a stock aluminum sulphate solution,of proper concentration or vice versa, these concentrations being such that'upon mixing the desired, composition isobtain'ed. To prepare the solutions in the area EFG, the silicate solution is added to the aluminumsulphate solution. Solutions hava ing the composition shown in the area DEGH can be prepared by adding the aluminum sulphate solution to the sodium silicate solution. I

In Fig. 2 the area bounded by the graph ABC represents the proportions of water, cadmium sulphate, and sodium silicate in which these ingredients can be mixed to produce a leak-stopping solution capable of functioning. according to the invention, Accordingto the graph, the propor ions are approximately 0.05 to l per cent of admium sulphate with from 0.05 to 26.5 per cent of sodium silicate. These solutions are formed by adding a stock silicate solution to a stock cadmium sulphate '?solution, the stock solutions being suitably diluted it necessary. In Fig. 3 the area bounded by the graphABC represents solution compositions having similar properties to those shown hi the previous graphs, the proportions of the constituentsbeing approximately 0.05 to 0.6 per cent of cupric chloride, with from 4 to 16.5 percent of sodium silicate. These solutions are formed by adding a stock silicate solution to a stock cupric chloride solution; the stock solutions being suitably diluted if necessary. v

In. Fig. 4 the area Bounded by the graph tion of about per cent of silicate by weight 5 ABCDE represents solution compositions having as a stock solution. Commercial water glass may be used in which the ratio of NazO to SiOptherein is 1:32, although other ratios may be employed. For the metal salt I may employ a soluble salt of any one of the aforementioned metals, 40" or from about 0.5 to 48.5 per cent of chromium such as the sulphate, chloride, or nitrate. I prefor to use the sulphate or chloride, because these are usually the cheapest, and in a concentration generally of about 20 per cent by weight for similar properties to those shown insthe previous graphs, the proportions of the constituents being approximately 0.05 to 1 per cent of chromium sulphate with from 1 to 7.5 per centof silicate,

the stock solution. Other concentrations of the .dilIu tedii' necessary.

stock solutions of either the silicate'orthe metal salt may be used, if desired, and, as will be seen hereinafter, are necessary in some instances for the preparation or'certaln of the leak-stopping Fig. 5 two series ot leak-stopping solutions 4 can be prepared according to the invention from the stock solutions oi sodium silicate and ferric chloride; The one series is shown by the graph solutionsinbrder that the proper proportion of ABC within the area of which the eflective prowater, metal salt, and-silicate will be obtained.

The manner in which the leak-stoppins solu-- tion-is prepared from the separate stock solutions of the constituents is important, it being essensaryl in a certain order-according to the 'metal salt employethand in some instances according to the proportions to be obtained in the resulting leak-stopping solution. The order of mixing as well as the proportions will bebetter understood go by referring to the diagrams.

In Fig. 1, the area bounded by the graph ABC and that bounded by DEFGH represent compositions of leak-stopping solutions containing aluminum sulphate in-the proportions which function according to the invention, Thus two series of solutions can be made from sodium silicate and aluminum sulphate. In one the solutions contain approximately 0.05 to 0.8 per cent I .or aluminum. sulphate with from 0.05 to 6 per cent g f sodium silicate (i. e. area ABC), in thej other approximately 0.05 to 23 per cent of aluminum sulphate is used withjrom 0.05 to 1.8 per cent of sodium silicate (i. e. area DEFGH).

tial to mix' the stock solutionsidiluted if neces- 65 efiective proportions are approximately from 0.05

to 1.8 per cent of sodium silicate with from 1.75 to 22 per cent of ferric chloride. In making these series of leak-stopping solutions the silicate solution is added to the ferric chloride solution.

leak-stopping solution compositions in which In Fig. 6 the graph ABC'represents similar manganese sulphate is present in amount of from about 0.05 to 0.75 per cent and sodium silicate from about 0.5 to 23 percent. These solutions are made by adding a stock manganese sulphate solution to one 9! sodium silicate, both stock' I solutions being suitably diluted if necessary.

In Flg. 7 two series oi'leak-stopplng compositions are shown whichman be prepared from tion .of stannic chloride. One series is represented by the area withinv the graph ABC in whichtapproximately 0.05 to 1.5. per cent of stannic chloride is used with from 1.5 to 22.5 per a sodium silicatesolution and an a'queo us solu- The solution compositions inthe area ABC can cent of sodium silicate. The other series isrepresented by the area within the graph DEF, in

which about 0.05 to 3 per cent of sodium silicate is used with about 1.5 to '74 per cent of stannic chloride. Each series of these solutions is made by adding a stock silicate solutionto one' of stannic chloride suitably'diluted if necessary.

In Fig. 8 leak-stopping compositions are shown by the'area within the graph ABC in which approximately 0.05 to 1 per cent of zinc sulphate is used with from about 0.2 to 21.5. per cent of sodium silicate, the order of mixing the stock solutions being to add the silicate solution to the zinc treated and a .cathode on the other and the whole immersed in the solution.- The electrolyzing current is then passed from the cathode to the anode through the solution and the por tion of the article to be-treated. A potential of about 1 to 4 volts is sufflcient, but other voltages may be used. In the treatment of earth, rock and the like as a stratum'penetrated bythe bore of a well; for example, an oil or gas well, so as to formed into asemi-rigid gel upon being sub-' jected to electrolysis, can be used according to my invention.- 'The proportions in which upon mixing the stock solutions of the enumerated constituents in the order prescribed leak-stopping solutions are produced having these special properties has been determined for a number of mixtures, those illustrated by the examples described above and shown by the respective areas enclosed by the graphs being typical. However, it is/evident that the proportions do not follow a simple law other than that contained in the three limitations above set forth, and excepting those proportions lying near the outside edges of the graphs where the minimum limiting propor- I tions occur at about 0.05 per cent for either the metal salt or the soluble silicate, as the case may be. The minimum limiting proportions are given by the straight linese AB and DEF on Fig. 1, AB on Fig. 2, AB on Fig. 3, AB and AE on Fig. 4,

, AB, AC, and DF on Fig. 5, AB on Fig.6, AB and DF on Fig. 7, and AB on Fig. 8, for example, and

the maximum proportions by the curved boundaries of the graphs.

Beyond the curved boundaries of the graphs (i. e. outside the area enclosed by the curved lines) mixtures are obtained which exhibit entirely different properties and either spontaneously become non-flowing gelatinous systems when prepared or shortly thereafter or form suspensions inwhichthe metal salt has been practically all precipitated and, therefore, cannot function in the unique manner of my solutions. When the proportion of the metal salt or of the silicate is less than 0.05 per cent, the solutlonnalthough fluid and generally free from .a fllterable precipitate, cannot be transformed into fii semi-rigid gel by electrolysis.

' To stopup leaks the solution, prepared in the a manner described-is maintained in contact with the leaking equipment in any convenient manner, as by filling the equipment or flowing the 'solution intoorthrough the leak. While in contact with the leaking place the solution is subjected to' electrolysis. This may be accomplished in various ways according to the nature ot the article'or equipment to be repaired. If

lthe article or equipment be of metal it may be made the .anode in the electric circuit which is [completed through a suitable cathode such as an iron plate immersed in the solution. Incases 'where the article itself is not an electric conductor, an anode may be placed onone side of, and preferablyin contact-with, the article to be stop leakage thereinto of water or'brine or to otherwise close the pore spaces, the solution may be introduced into the well and thence into the stratum in any suitable manner and electrolyzed in situ, pressure being applied if necessary to hold the solution in place. Electrolysis may be efiected b -applying a suflicient potential across an electrode lowered into the well bore in electrical contact withthe solution and another electrode sunk in the surrounding earth- The electrode man well is preferably madethe anode. Voltages up to 100 or more may be used so as to give an adequate current density in the solution in the surrounding earth'or rock to bring about gelation of the solution.

In some instances it is not always necessary to apply an external source ofpotential to effect the electrolysis, as when the article comprises dissimilar metals, and the'leak to be repaired occurs at or near the junction of such metals. For example, a leak occurring in the joint' of a lead-calked iron pipe can be readily rendered fluid tight by merely filling the interior of the pipe with the leak-stopping solution and applying suflicien t pressure upon the solution, if necessary, to introduce it into'the leak. The potential produced by contact of the solution with both the lead of the calking -and the iron walls of the pipe, which are electrically connected together by virtue of being in contact with each other, is sufficient to bring about the electrolysis and deposition of the leak-sealingdeposit in a comparatively short time.

In some instances the metal itself of a leaking article to be repaired may be so nonhomogeneous as to set up potential differences when the leak-stopping solution is brought into contact therewith suflicient to bring-about deposition of a sealing deposit in situ.

When the leaks to be stopped up are relatively large and would permit a substantial loss of leakstopping solution during the deposition of the sealing gel, as when sealing leaks in alarge'pipe system or the like, or highly porous earth or rockformations, such losses may be reduced or prevented by adding to the leak-stopping solution a moderate percentage of fibrous asbestos.

After the sealing gel deposit is obtained-to the desired extent, that part of the solution which has not become transformed into a gel may be removed and stored in a glass. or wooden vessel for reuse. further treat the deposited gel with an aqueous solution-of calcium chloride containing from 5 to 20 per cent of CaClz which has the eifect of further hardening it and resistant to erosion.

-The following examples are further illustrations of the method of carrying out the invention:

Example 1 2 43 gallons of a 20 per cent stock solution of sodium silicate was added to 0.13 gallon of a 20 per cent stock solution of aluminum sulphate It is an advantagein some instances to thereby making it more resulting leak-stopping solution. (approximately gallons) was substantially free from fllterable precipitate and substantially as fluid as water.

- The solution-was then introduced into a section of cast iron pipe having a longitudinal crack therein. so as to pass the solution into the crack and allow the formation therein of a leak-sealing deposit, upon being subjected to electrolysis. In this case it was found that there was a sufllcient potential developed by the solution in contact with the iron pipe itself. due to inhomogeneity of the metalto effect electrolysis without the need for applying an external E. M. F. After the leaksealing deposit occurred, the solution was withdrawn from the pipe and then it was flushed with water. On testing the pipe for leakage after the treatment it was foundto be able to withstand more than 75 lbs/sq. in. water pressure without leakage. l a

. Example 2 In this test there was treated a section of a cast ironhub and spigot water main. The main was 24 inches in diameter and 1249 feet long'laid across a river in the river bed and normally car'- ried 3.to 4 million gallons of water per day. main developed leakage amounting to about th. gallons per hour. at 60 pounds per square inch. Most 'of the leakage appeared to be at the leari 25, 1938 on which Patent No. 2,188,311 was issued January 30, 1940. n

' I therefore particularly point out and distinctly claim as my invention:

1. In a method of producing a leak-sealing deposit, the steps which consist in introducing into the space to be sealed an aqueous solution containing a soluble alkali metal silicate and a watersoluble inorganic metal salt selected from the group consisting of 'the water-soluble inorganic salts of aluminum, cadmium, trivalent chromium, divalent copper, trivalent iron, divalent manganese, tetravalent .tin, zinc, in proportions such sist in introducing into the joint and maintaining calked joints, Of which there were 112 as shown by water meter readings and by closing each end of the main and displacing the water therefrom by air, bubblesof which were'observed torise to the rivers surface above many of'the joints. In. treating this pain, the .water therein; approximately 33,000 gallons, .was displaced by introducing thereinto my leak-stopping solution comprising sodium silicate, aluminum sulphate, and water in the relative proportions of about 5 per-cent, 0.7

in contact with the inner wall'of the pipe and the lead-calking an aqueous solution containing a soluble alkali-metal silicate and a water-soluble inorganic metal salt selected from the group consisting of the water-soluble inorganic salts of aluminum, cadmium, trivalent chromium, divalent copper, trivalent iron, divalent manganese, tetravalent tin, zinc,'in proportions such that the said solution is readily fllterable, normally remains fluid, and is transformable into a semirigid gel upon subjection to electrolysis; whereby per cent, and 94.3 per cent, respectively. The 40 leak-stopping solution was made up by adding 4000 gallons of a -5 per cent sodium silicate solution to 36,000 gallons 015 water mixedtogether in batches of 900 gallons each and to each batch was added 25 gallons of an aqueous solution of aluminum sulphate containing 2.4 pounds per gallon, while the batch of diluted sodium silicate was vigorously agitated. 10 pounds of fibrous asbestos was incorporated in each batch. After electrolysis of the solution occurs due to the potential diflerence between the walls or the pipe 35 and the lead-calk1n8, producing a semi-rigid gel in situ sealing the joint. 1

3. In a method of repairing a leak in a metal system designed to hold or transmit a fluid, the steps which consist'inmaintaining in contact with the leaking portions of the system an aqueous solution containing a soluble alkali-metal silicate and a water-soluble inorganic metal salt selected from the, group consisting of the watersoluble inorganic salts of aluminum, cadmium, trivalent chromium, divalent copper, trivalent iron, diva l nt manganese, tetravalent tin, 'zinc, in proportions such that the said solution is readily illterable, normally remains fluid, and is transthe main was filled, which required the intro- 5 duction thereinto of about 40,000 gallons of solu-' tion, some 7000 gallons of which was lost through the leaks while being plugged by the solution,

pressure was applied to the solution and gradually 1 l increased in intensity at the rate of 5 pounds,

per hour until a pressure of ,85 pounds per square inch was reached in the main. This pressure was then maintained for about 10 hours by pumping additional amounts of the leak-plugging solution into the main to compensate for losses treatment. At the end of this period the leakage had practically ceased. The solution was then displaced with a 4 per cent-aqueous solution of calcium chloride, upon'which pressure was, ap-

plied in gradually increasing intensity until 65 65 pounds per square inch was-reached. This pressure was maintained for-about 18 hours during which practically no leakage of solution was observed. The main was then flushed with .water and given a final water pressure test at between 70 to pounds per square inch. It was found that substantially no leakage occurred.

This application is a continuation-in-part of my application Serial No. 186,866, filed January Y formable into a semi-rigid gel upon subjection to electrolysis, and subjecting the said solution tq electrolysis; whereby a semi-rigid gel is produced in situ sealing the leak.

4. The methodof sealing a lead-calked joint of an ironipipe-which comprises maintaining in contact withthe inner wall of the iron pipe and the lead-calking an aqueous solution formed by the admixture of sodium silicate, aluminum'sulphate, and water in proportion such that the said solu- .tion is readily filterable, normally remains fluid,

and forms a gel upon subjection to electrolysis; whereby electrolysis of the'solution occurs due to the potential diii'erence between the wall of the pipe and the lead-calking, producing a gel in situ sealing the joint. 3 I

5. The-method of producing in a place to be sealed which comprises'introducing into the place 'an aqueous solution containing from 0.05 to 0.8 per cent of aluminum sulphate and from 0.05 to 6 per cent of sodiurn silicate, and transforming the said solution intoa gel in situ by electrolysis sealing .the said place.

HYANSIA. REIMERS.

a sealing deposit 

